ES2751367T3 - Modular photochemical flow reactor system - Google Patents

Abstract

A modular photochemical reactor system (10) including: a plurality of fluidic modules (20) each having a flat shape with first and second major surfaces (22, 24), each of said first and second major surfaces (22, 24) having 24) a free surface area (22F, 24F) devoid of inlet and outlet ports, and each having i) a flat central layer of process fluid (30) and ii) two outer flat layers of thermal control fluid (40 ) to contain flowing thermal control fluid, said planar central layer of process fluid (30) and said two outer planar layers of thermal control fluid (40) being disposed between said first and second major surfaces (22, 24) and being at least partially transparent to radiation at at least some wavelengths in the UV and / or visible spectrum; and a plurality of lighting modules (50), each having a flat shape with first and second major surfaces (52, 54), and each including at least one first set (60) of semiconductor emitters (70), being placed said emitters (70) capable of emitting at visible and / or UV wavelengths to emit from or through the first main surface (52) to the free surface area (22F or 24F) of one of the first and second main surfaces ( 22, 24) of a fluidic module (20), where said first set (60) of semiconductor emitters (70) includes at least a first emitter (72) and a second emitter (74), the first emitter (72) being capable of emitting at a first central wavelength and the second emitter (74) capable of emitting at a second central wavelength, said first and second central wavelengths being different from each other.

Description

DESCRIPTION

Modular photochemical flow reactor system

Countryside

The present disclosure relates to flow reactors and flow processes performed therewith, in particular to a high production, flexible, modular photochemical flow reactor system.

Background

The authors of the present invention and / or their colleagues previously developed flow reactors to perform chemical reactions. These flow reactors can typically employ fluidic modules that can take the form of a multilayer glass structure. A representation of one embodiment of such a fluidic module 20 is shown in Figure 1 in perspective view. Representations of some features of additional embodiments of such fluidic modules 20 are shown in Figures 2 and 3 in cross-sectional views. Fluidic modules 20 of the type or types shown in Figures 1-3 generally have a flat shape and first and second main surfaces 22, 24 (surface 24 being below module 20 in the perspective view of figure 1). Reagents or process fluids circulate within "microchannels", generally millimeter or submillimeter wafer channels defined within a generally flat process fluid layer 30. Module 20 further includes two outer flat layers of thermal control fluid 40 for containing fluid thermal control fluid, with the process fluid layer 30 positioned between the two thermal control fluid layers 40.

Process fluid inlet and outlet ports 32 allow process fluid to be supplied and removed (one of the ports 32, the outlet port in this case, is not visible in Figure 1 because it is on the main surface facing down 24, opposite the upward-facing hole 32). The thermal fluid inlet and outlet ports 42 allow supply and removal of thermal control fluid. All inlet and outlet holes 32, 42 are located on one of the first and second major surfaces at one or more of their edges (at edge 26 in the case of the Figure 1 embodiment), leaving a free surface area 22F (and a corresponding free surface area 24F, below and not visible in Figure 1) free of inlet and outlet holes.

Scale-up from laboratory-scale processes to production scale is enabled by a range of various fluidic module sizes 20. To provide adequate residence time, for a given required flow rate, a certain amount of internal volume is required . The increased total internal volume, when necessary, is obtained by connecting several fluidic modules 20 in series to form a reactor. Therefore, a reactor is typically made up of several fluidic modules 20. Each fluidic module 20 can have a specific function, such as preheating, premixing, mixing, residence time provision, rapid cooling, etc. Since modules 20 can be formed from glass, photochemistry is a potentially useful application, since glass is at least partially transparent at wavelengths of interest for photochemistry in UV and visible spectra.

Numerous prior art documents describe photochemical reactors. US Patent Application 2012/0228236 describes a direct illuminated photochemical fluid treatment reactor with LED assemblies. The LED light source can be mounted on fluid-cooled heat sink blocks. The heat sink may be configured to use the treated fluid as its coolant. Fluid cooling is not described during illumination. US Patent Application 2010/0255458 describes different embodiments of bioreactors with light distribution elements. US Patent Application 2013/0102069 describes a bioreactor that uses a light emitting diode (LED) lighting system to provide light at least partially for an algae. US Patent Application 2014/0050630 describes a microreactor for photoreactions. US Patent Application 2012/0091489 refers to a photoemitting device.

Summary

The invention relates to a modular photochemical reactor system including a plurality of fluidic modules, each having a flat shape with first and second main surfaces, each of said first and second main surfaces having a free surface area devoid of inlet holes and outlet, and each including: i) a flat central process fluid layer to contain flowing process fluid, ii) two outer flat layers of thermal control fluid to contain flowing thermal control fluid; said flat central layer of process fluid and said two outer flat layers of thermal control fluid being disposed between said first and second main surfaces and being at least partially transparent to radiation at least some wavelengths in the UV spectrum and / or visible. The system further includes a plurality of lighting modules, each having a flat shape with first and second main surfaces, and each including at least a first set of semiconductor emitters, said emitters being positioned, capable of emitting at wavelengths visible and / or UV, to emit from or through the first main surface to the free surface area of one of the first and second main surfaces of a fluidic module, where said first set of semiconductor emitters includes at least a first emitter and a second emitter, the first emitter being capable of emitting at a first central wavelength and the second emitter being capable of emitting at a second central wavelength, said first and second central wavelengths being different from each other. Said fluidic modules and said lighting modules are arranged so that at least some of said fluidic modules are capable of benefiting from the irradiation from said lighting modules.

The use of semiconductor emitters, desirably LEDs, makes it possible to employ sharply defined wavelengths with the possibility of increasing the performance of a reaction or decreasing the production of unwanted by-products that can be promoted by unwanted wavelengths present in sources that have a broader spectrum. Providing at least first and second emitters of different central wavelengths allows for easy experimentation and optimization between the two wavelengths, as well as potentially increased performance of reactions that can benefit from light at more than one wavelength. The resulting reactor assembled from the described system is both flexibly and compactly reconfigurable, while also isolating the thermal output from the reagent or process fluid emitters. The system of the present invention and the reactor formed therefrom also provide the ability to switch illumination wavelengths, or, more generally, to alter the spectral composition of illumination without disassembly of the reactor, such that Reaction tests and characterization are carried out more easily.

Other variations and specific advantages are explained or will be apparent from the following description. The foregoing general description and the following detailed description show specific embodiments, and are intended to provide an overview or structure for understanding the nature and character of the claims.

Brief description of the drawings

Figure 1 is a perspective view of an embodiment of a useful fluidic module within the system currently described.

Figures 2 and 3 are cross-sectional views of additional embodiments of useful fluidic modules within the system currently described.

Fig. 4 is an expanded perspective mounting view of one embodiment of a useful lighting module within the system currently described.

Figures 5A and 5B are schematic cross-sectional views of additional embodiments of useful lighting modules within the system currently described.

Figure 6 is a perspective view of an embodiment of a support frame or core of a useful lighting module within the system currently described.

Figures 7A and 7B are schematic plan view representations of alternative embodiments of emitter assemblies of a useful lighting module within the system currently described.

Figure 8 is a perspective view of an embodiment of a partially assembled reactor composed of components of the system currently described.

Figure 9 is a perspective view of the reactor of Figure 8 with some additional components included. Detailed description

A modular photochemical reactor system 10 depicted in perspective view in Figure 9 includes a plurality of fluidic modules 20, each of the fluidic modules 20 of said plurality having a flat shape as seen in Figure 1, with first major surfaces and second 22, 24. Each fluidic module 20 of said plurality includes, also as seen in Figure 1, and additionally in Figures 2 and 3, a flat central layer of process fluid 30 to contain said flowing process fluid, and two outer flat layers of thermal control fluid 40 to contain flowing thermal control fluid. The process fluid layer 30 is positioned between the two thermal control fluid layers 40. The process fluid layer 30 and the two thermal control fluid layers 40 are at least partially transparent to radiation at least some lengths wave in the UV and / or visible spectrum. In operation of the fluidic modules 20, substantially transparent thermal control fluids, such as water or ethanol, may desirably be used.

Each fluidic module 20 of said plurality further includes process fluid inlet and outlet ports 32 for supplying and withdrawing process fluid and thermal fluid inlet and outlet ports 42 for supplying and removing thermal control fluid, the orifices being located fluid inlet and outlet 32 1) on one of the first and second main surfaces 22, 24 on one or more of its edges 26, or 2) on a surface 28 of the fluidic module 20 distinct from their first and second main surfaces 22, 24, in any case leaving a free surface area 22F, 24F of the first and second main surfaces 22, 24 free of inlet and outlet holes, said free surface area 22 ^{f including} , 24F at least 50%, desirably at least 75%, of the total area of the respective first or second main surface 22, 24.

The modular photochemical reactor system 10 depicted in perspective view in FIG. 9 further includes a plurality of lighting modules 50 such as those depicted in the perspective view embodiments of FIG. 4 and the cross-sectional views of FIGS. 5A and 5B. Each of the lighting modules 50 of said plurality has a flat shape with first and second main surfaces 52, 54, and each includes at least a first set 60 of semiconductor emitters 70, said emitters 70 being capable of emitting at lengths and / or UV waveforms positioned to emit from or through the first main surface 52. Furthermore, said first set 60 of semiconductor emitters 70 includes at least a first emitter 72 and a second emitter 74, the first emitter being 72 capable of emitting at a first central wavelength and the second emitter 74 being capable of emitting at a second central wavelength, where said first and second central wavelengths differ from each other.

More details of one embodiment of a lighting module are shown in the exploded perspective view of FIG. 4. A support frame or core 90 of the lighting module 50 includes inlet and outlet ports 94 for supplying cooling fluid to the lighting module. 50. The core 90 together with a seal 64 and cover 66, when assembled and fixed together in the order shown, forms a heat exchanger 96 to cool the emitters 70 of the array 60 of emitters 70. The emitters 70 are mounted ( for example, by a welding process or other mounting process or structure) on a mounting sheet 71, which is mounted on the cover 66. Alternatively, as in the additional embodiments shown in cross section in Figures 5A and 5B, the Mounting sheet 71 for emitters 70 can function as a cover to cover fluid channels in core 90 such that a separate cover is not used a 66, as in the embodiment of Figure 4. A light shield or frame 97 may be mounted in order to surround the assembly 60 on its sides, and a protector window 98 may be mounted on the protector 97. The window shield may be of quartz, glass, or any other desirably transparent material relative to the wavelength or wavelengths employed by lighting module 50, and may optionally include a rough structure or similar optical element to function as a diffuser Optical to equalize lighting provided by lighting module 50. As another optional alternative, window 98 and frame 97 can also cooperate to form a seal on assembly 60, and the sealed volume can be filled with an inert gas, such as as argon or low reactivity gas such as nitrogen. This would serve to protect the emitters from any airborne chemicals or chemicals otherwise present in or near the guard window 98.

Figures 5A and 5B are schematic cross-sectional views of additional embodiments of lighting modules 50. In Figure 5A it can be seen more clearly (than in Figure 4) that a lighting module 50 according to the present description may desirably include both a first set (of emitters 70) 60 as a second set (of emitters 70) 80, on opposite first and second main surfaces 52, 54 of the lighting module 50. A single core 90 may have two sides each with a surface for supporting each of the two assemblies 60, 80. The assembly or assemblies can be retained by a clip or flange 62. As generally illustrated in Figure 5B, the system currently described also desirably includes lighting modules 50 having only one set 60, rather than two sets 60, 80 as in Figure 5A.

FIG. 6 depicts a perspective view of one embodiment of a core 90, including a support surface 91 for the emitter assembly 60 or the cover 66, on the support surface of which there are recessed channels 93 for containing flowing coolant fluid.

Figures 7A and 7B are schematic plan view representations of alternative embodiments of emitter assemblies 60 (and 80) of a lighting module 50, such as those of Figures 4, 5A and 5B. In the embodiment of Figure 7A, the emitters 70 are in the form of individually packaged emitters (or individually packaged LEDs) 78, while in the embodiment of Figure 7B the emitters 70 are in the form of groups of 79 emitters (such as "multichip" LEDs ") (of different types 72, 74, 76), at least two types at least, packaged together. In both embodiments, there is at least a first emitter 72 and a second emitter 74, the second emitter 74 having a second center wavelength different from a first center wavelength of the first emitter 72. Optionally, assembly 60 (or 80) it may further include at least a third emitter 76 capable of emitting at a third central wavelength, the third central wavelength being different from each of the first and second central wavelengths. You can also use more than three different emitters or types of emitters. Furthermore, grouped emitters (or groups of emitters) 79 within the same set can be used as individual emitters.

Regardless of the number of different types and if they are packaged together, it is also desirable that the various different types of emitters 72, 74, 76 be independently controllable by switch or controller or receiver 100, via respective control lines and / or power 102a , 102b, 102c (generally labeled 102). Preferably, the various emitter subsets, each consisting of emitters of the same wavelength, are independently controllable by switch or controller or receiver. The issuers of the The same wavelength or central wavelength in an array are desirably collectively controlled. Independent control over various wavelengths allows for easy reaction characterization or other experimentation or reaction control involving the use of various wavelengths, without having to disassemble the reactor or any component.

The emitters 70 are desirably LEDs. According to one embodiment, the assembly includes a printed circuit board on which the emitters are mounted. Furthermore, they are desirably capable of providing at least 40 mW / cm2 of homogeneous irradiation to the free surface area 22F, 24F of the first or second major surface 22, 24 of a fluidic module 20, more desirably at least 50 mW / cm2. The LEDs may be high power LEDs, or their density in the array may be sufficient to achieve the desired irradiation. A desired degree of irradiance homogeneity can be achieved through the density of LEDs in the array, or through an optical diffuser.

Figures 8 and 9 show perspective views illustrating an embodiment of some ways in which the system 10 of the present description can be mounted in a reactor 12. In Figures 8 and 9, the fluidic modules 20 and the lighting modules 50 they are supported on a support or reactor mount 104, in this case in the form of a beam. Alternatively, the fluidic modules 20 and the lighting modules 50 can be supported on 2 separate supports or mounts, and the lighting modules 50 and their support or mounting can enter and exit the reactor in order to facilitate the maintenance of the system. The lighting modules 50 of these embodiments include both two-sided lighting modules 50a and single-sided lighting modules 50b. In Figure 8, the reactor 12 is shown without the fluidic modules 20. Figure 9 depicts the position of multiple fluidic modules 20 between the radioactive faces of the lighting modules 50.

The reactors 12 formed from system 10 are both flexibly reconfigurable and compact, while well isolating the thermal output of the emitters from the reagent or fluid processes, first of all, because of the use of semiconductor emitters such as LEDs in which the energy conversion efficiency is reasonably high, as opposed to lamps and other similar sources, and, secondly, because of the use of heat exchanger 96 which is capable of drawing up to multiple hundreds of watts, and, thirdly, because the process fluid layer 30 of the fluidic module 20 is surrounded on both sides by a thermal control fluid layer 40 through which the incoming illumination reaches, thereby providing significant isolation from the heat generated by emitters 70 or in them. The reactors 12 formed from the system 10 also allow the LED emitters to operate at a low temperature (lower than the ambient temperature and the operating temperature of the fluidic module, by using heat exchangers 96, resulting in a higher emitted intensity and a longer duration. of the LEDs.

The system of the present invention and the reactor formed from it also provides the ability to switch illumination wavelengths, or, more generally, to alter the spectral composition of illumination without disassembly of the reactor, such that reaction tests and characterization are more easily performed. It is advantageous to be able to perform photochemical reactions in a flow reactor that is compact, but flexible, both in reactor structure or design and in the radiation delivered. The wavelength of light of interest is primarily near violet UV light between 300 and 450nm, but other UV or visible wavelengths may also be of interest.

Illumination of the operating fluid layer 30 from both sides of the fluidic modules 20, through the thermal control layers 40, not only helps provide thermal insulation, but also provides a large amount of illumination to the process fluid and can allow more uniform penetration through the depth of the process channel, relative to illuminating only on a main surface of the fluidic module 20.

It should be noted that not all fluidic modules 20 in a given reactor will necessarily require or benefit from irradiation; consequently, some fluidic modules may not be illuminated within the same reactor as some others are. In other words, the lighting is scalable independently or in conjunction with the number of fluidic modules.

Therefore, different types of chemicals can be made with the same lighting solution, without any equipment change, without any maintenance. This is not specific 1 wavelength specific equipment.

By using spectrally narrower light from semiconductor sources, chemists can be better understood and therefore optimized. The exact wavelength of semiconductor sources allows for more product selectivity. The duration of the light source will also be long.

The methods and / or devices described herein are generally useful in performing any process involving mixing, separation, extraction, crystallization, precipitation, or other processing of fluids or fluid mixtures, including multiphase fluid mixtures - and including fluids or fluid mixtures. including multiphase fluid mixtures that also contain solids - within a microstructure. Processing may include a physical process, a chemical reaction defined as a process that results in the interconversion of organic, inorganic, or both organic and inorganic, and desirably includes a favored chemical, physical, or biological process or reaction in the presence of light, of any wavelength, i.e. photoreactions, whether photosensitized, photoinitiated (as in photoinitiated radical reactions), photoactivated , photocatalytic, photosynthetic or others). A non-limiting list of light-assisted or light-assisted reactions of possible interest includes photoisomerizations, rearrangements, photoreductions, cyclizations, 2 + 2 cycloadditions, 4 + 2 cycloadditions, 4 + 4 cycloadditions, 1,3-dipole cycloadditions, sigmatropic changes (which could lead to cyclization), photooxidation, photocivibration of protecting groups or bonds, photohalogenations (photoclorations, photobrominations), photosulfoclorations, photosulfoxidations, photopolymerizations, photonitrosations, photodecarboxylations, photosynthesis of previtamin D, decomposition of arton compounds, Barton-type reactions. In addition, the following non-limiting list of reactions can be made with the methods and / or devices described: oxidation; reduction; substitution; elimination; addition; ligand exchange; metal exchange; and ion exchange. More specifically, reactions from any of the following non-limiting lists can be performed with the methods and / or devices described: polymerization; alkylation; dealkylation; nitration; peroxidation; sulfoxidation; epoxidation; ammoxidation; hydrogenation; dehydrogenation; organometallic reactions; precious metal chemistry / homogeneous catalyst reactions; carbonylation; thiocarbonylation; alkoxylation; halogenation; dehydrohalogenation; dehalogenation; hydroformylation; carboxylation; decarboxylation; amination; arylation; peptide coupling; aldol condensation; cyclocondensation; dehydrocyclization; esterification; amidation; heterocyclic synthesis; dehydration; alcohololysis; hydrolysis; ammonolysis; etherification; enzymatic synthesis; cetalization; saponification; isomerization; quaternization; formylation; phase transfer reactions; silylations; nitrile synthesis; phosphorylation; ozonolysis; azide chemistry; metathesis; hydrosilylation; coupling reactions and enzymatic reactions ..

The foregoing description provides exemplary embodiments to facilitate understanding of the nature and character of the claims. It will be apparent to those skilled in the art that various modifications can be made in these embodiments without departing from the scope of the appended claims.

Claims (10)

1. A modular photochemical reactor system (10) including: a plurality of fluidic modules (20) each having a flat shape with first and second major surfaces (22, 24), each of said first and second major surfaces (22, 24) having a free surface area (22F, 24F) lacking inlet and outlet ports, and each having i) a flat central layer of process fluid (30) and ii) two outer flat layers of thermal control fluid (40) to contain flowing thermal control fluid, being arranged said central flat layer of process fluid (30) and said two outer flat layers of thermal control fluid (40) between said first and second main surfaces (22, 24) and being at least partially transparent to radiation at least some lengths wave in the UV and / or visible spectrum; and a plurality of lighting modules (50), each having a flat shape with first and second main surfaces (52, 54), and each including at least a first set (60) of semiconductor emitters (70), being said emitters (70) capable of emitting at visible and / or UV wavelengths placed to emit from or through the first main surface (52) to the free surface area (22F or 24F) of one of the first and second main surfaces ( 22, 24) of a fluidic module (20), wherein said first set (60) of semiconductor emitters (70) includes at least a first emitter (72) and a second emitter (74), the first emitter (72) being capable of emitting at a first central wavelength and the second emitter (74) capable of emitting at a second central wavelength, said first and second central wavelengths being different from each other. 2. The system (10) according to claim 1, wherein said first set (60) further includes at least a third emitter (76) capable of emitting on a third central wavelength, said third central wavelength being different from each one of the first and second central wavelengths. 3. The system (10) according to either of claims 1 and 2, wherein the emitters (70) include individually packaged emitters (78). The system (10) according to any of claims 1-3, where the emitters (70) include emitters packaged in groups (79) and where said groups (79) contain at least a first emitter (72) and at least one second emitter (74). The system (10) according to any of claims 1-4, wherein said at least one first emitter (72) within said first set (60) is connected to a first power or control line (102a) and said at least a second emitter (74) within said first assembly (60) is connected to a second power or control line (102b). The system (10) according to any of claims 1-5, wherein the plurality of lighting modules (50) includes at least one lighting module (50a) which further includes a second set (80) of semiconductor emitters ( 70) capable of emitting at visible and / or UV wavelengths and positioned to emit from or through the second main surface (54), said second set (80) of semiconductor emitters (70) including at least a first emitter ( 72) and a second emitter (74). The system (10) according to claim 6, wherein said at least one lighting module (50a) of said plurality of lighting modules (50) further includes a heat exchanger (96) including a passage of cooling fluid ( 92) having inlet and outlet holes (94), the heat exchanger (96) being in thermal contact with the emitters (70) of the first set (60) and with the emitters (70) of the second set (80). The system (10) according to any of claims 1-5, wherein said lighting modules (50) of said plurality further include a heat exchanger (96) including a cooling fluid passage (92) having holes for inlet and outlet (94), the heat exchanger (96) being in thermal contact with the emitters (70) of the first set (60). 9. The system (10) according to any claim 1-8, where the emitters (70) are LEDs. The system (10) according to claim 9, wherein the LEDs are capable of providing at least 40 mW / cm2 to the free surface area (22F, 24F) of the first or second main surface (22, 24) of a module fluidic (20).